Herbicidal compositions of polyoxyalkylene alkylamine surfactants having reduced eye irritation

ABSTRACT

There are provided compositions of certain polyoxyalkylene alkylamine surfactants having eye irritation reduced by the addition of an effective amount of a sulfated polyoxyalkylene alkylphenol alcohol sulfate, polyoxyalkylene alcohol sulfate, mono- or dialcohol phosphate mono- or di-(polyoxyalkylene alcohol) phosphate, polyoxyalkylene alkylphenol carboxylate or polyoxyalkylene alcohol carboxylate surfactant. Also provided are pesticidal, particularly herbicidal, compositions comprising polyoxyalkylene alkylamine surfactants having eye irritation reduced by addition of these eye irritation reducing compounds.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of application Ser. No. 08/932,503filed Sep. 18, 1997, which is a continuation of application Ser. No.08/358,274 filed Dec. 19, 1994 (U.S. Pat. No. 5,703,015), which is acontinuation-in-part of application Ser. No. 08/101,214 filed Aug. 4,1993, now abandoned, which is a continuation of application Ser. No.07/565,816 filed Aug. 9, 1990, now abandoned.

BACKGROUND OF THE INVENTION

The present invention generally relates to novel surfactantcompositions, their preparation and to compositions containing thesenovel surfactant compositions, together with a pesticide, particularly aherbicide. More particularly, an important aspect of this invention isdirected to surfactant compositions having reduced eye irritancy whichare useful in the preparation of herbicidal compositions having reducedeye irritation properties in addition to their herbicidal effectiveness.In this regard, a further important aspect of the present inventionconcerns surfactant compositions which are effective in the formulationof glyphosate-containing herbicidal compositions or pesticidalcompositions of other water soluble active ingredients. A method ofusing the herbicidal compositions is also provided.

Numerous organic pesticides; i.e., chemicals that are useful in thecontrol of bacteria, insects, fungi, weeds and the like, have beendeveloped in recent years. These pesticides, especially herbicides, havefound use in agriculture, as well as for household applications.Regardless of whether the pesticide is water soluble or water insoluble,it is desirable to use the same in an aqueous medium rather than in anon-aqueous solvent which is more difficult to use by the formulator andapplicator, could cause environmental damage, is more costly and is ingeneral less desirable. Water-based dispersions, emulsions and/orsolutions can be prepared from most pesticides using selectedsurfactants. Proper selection of the surfactant can also improve theefficacy of pesticidal compositions.

Surfactants are useful in the preparation of herbicidal compositionswhether the herbicide is water soluble or insoluble. When the herbicideis water insoluble, the surfactant can be used to make a waterdispersible herbicide composition. When the herbicide is water soluble,the surfactant can often be used to improve the herbicidal effectivenessof the herbicidal composition.

One class of surfactants that has found success in the preparation ofherbicidal compositions includes the polyoxyalkylene alkylamines, suchas, for example, ethoxylated tallowamine. These compounds have thenecessary surface activity so that many otherwise water insolubleherbicides, as well as water soluble herbicides, can be formulated intoconcentrates which will form useful dispersions, emulsions and solutionsin water. Herbicides formulated into dispersions, emulsions andsolutions using these surfactants often have improved herbicidalproperties. This class of surfactants is well known to potentiate theherbicidal activity of glyphosate.

While the polyoxyalkylene alkylamine compounds have excellent surfactantproperties which often enhance the efficacy of phytotoxicants, theyunfortunately are eye irritants and must be used with a high degree ofcaution.

Reducing or eliminating the eye irritancy of the polyoxyalkylenealkylamine surfactants used with pesticides, without reducing theefficacy of the pesticidal compositions containing the surfactants, is ahighly desirable end. The protection of the applicator and personnelpreparing the surfactant and pesticidal compositions from eye damage isof paramount importance. Reducing the eye irritancy of the surfactantand pesticidal compositions containing the surfactant, increases the usethat can be made of such products while lessening the possibility ofinjury to personnel handling and using them.

In order to obtain surfactant compositions having the desiredcharacteristics needed for use with the numerous pesticides on themarket, various combinations of surfactants have been previously made.

U.S. Pat. No. 4,313,847 describes three component surfactantcompositions including a polyoxyalkylene alkyl or alkylaryl etherphosphate ester, a polyoxyalkylene alkylamine and a material selectedfrom the group consisting of nonionic polyoxylated surfactants,polyhydric alcohol esters and polyoxyalkylene glycols. According to thispatent, the three component composition is an improved emulsifierenhancing the use of an emulsion containing a water insoluble herbicide.

Combinations of emulsifiers are also shown in the following patents:U.S. Pat. No. 2,872,368 discloses a polyoxyethylene glycol or apolyoxypropylene glycol in combination with an oil soluble alkalineearth metal salt of an alkylated naphthalene sulfonic acid; U.S. Pat.No. 3,683,078 discloses emulsifier compositions having threecomponents: 1) the condensation product of an alkylphenol and analkylene oxide, 2) a sulfonate salt and 3) a polyoxyalkylene derivativeof an alkanol; and U.S. Pat. No. 3,071,550 discloses selected sulfonatesin combination with an aliphatic diester of unsaturated carboxylic acidsand the condensation product of glycerin and from about 15 to about 27moles of ethylene oxide.

As stated in British Patent No. 769,736, due to the diverse nature ofpesticides, the selection of the proper emulsifying agent in anyparticular instance is difficult. This patent shows combinations of asurface active alkylaryl polyoxyalkylene glycol ether and a watersoluble salt of a phosphate or sulfate ester as one of the ethers. ThisBritish patent, like the preceding patents, shows the continuing needfor a multitude of surfactants many of which are obtained bycombinations of known materials.

It is known to formulate aqueous solutions of the herbicide glyphosateand sulfated nonalkoxylated C₈ -C₁₀ alkyl alcohol surfactants. Suchherbicidal compositions have been sold by Monsanto Company of St. Louis,Mo., for example, under the trademark PONDMASTER.

None of the foregoing patents discusses the problem of surfactants beingeye irritants. Yet this is an important factor which must be taken intoconsideration when preparing and using compositions containingpolyoxyalkylene alkylamine surfactants. Thus, there exists an importantneed for such compositions having reduced eye irritancy withoutsacrifice of pesticidal activity.

Perhaps the most widely used herbicide worldwide is glyphosate, whichchemically is N-phosphonomethylglycine. This product is normally used inan agriculturally acceptable form, such as a water soluble salt; e.g.,the isopropylamine salt. For certain commercial uses glyphosate is madeinto a herbicidal concentrate composition containing a surfactant, whichcan then be diluted with water for use by the applicator. Often usedsurfactants for the preparation of these compositions are theaforementioned polyoxyalkylene alkylamines, especially ethoxylatedtallowamine. European Patent 290,416 discloses combinations ofsolubilized glyphosate, equivalent to at least 40 grams per liter ofglyphosate acid, and alkoxylated alkylamine surfactants in a ratio ofthe solubilized glyphosate (expressed as glyphosate acid equivalent) toamine surfactant of from about 1:1.75 to about 6:1. According to thisEuropean Patent, the compositions permit a reduction in the surfactantto glyphosate ratio without loss of herbicidal effectiveness. Clearly,the use of compositions containing glyphosate and alkoxylatedtallowamine having reduced eye irritation is of considerable importance.The invention described herein presents a method of improving the highlydesirable properties of such compositions.

The U.S. Environmental Protection Agency requires that currentlycommercial aqueous concentrate glyphosate herbicide solutions having analkoxylated alkylamine surfactant be labelled to contain a precautionarystatement that the solution can cause eye burns. To remedy or amelioratethis hazard is a desideratum of long standing.

It is therefore an object of the present invention to provide newcompositions containing an alkoxylated alkylamine surfactant.

Another object of the present invention is to provide suchsurfactant-containing compositions that can be used to preparepesticidal compositions, particularly herbicidal compositions havingsignificantly reduced eye irritancy.

Another object of the present invention is to provide new methods forthe preparation of compositions containing an alkoxylated alkylaminesurfactant and having reduced eye irritancy.

Another object of the present invention is to provide compositions ofthe herbicide glyphosate having agriculturally acceptable herbicidalefficacy and reduced eye irritancy.

Another object of the present invention is to provide new methods forcontrolling the growth of weeds and other vegetation.

Other objects of the present invention will become apparent from thefollowing description.

SUMMARY OF THE INVENTION

The present invention is directed to a surfactant composition comprisinga polyoxyalkylene alkylamine having at least about 2 moles of analkylene oxide group and reduced eye irritancy. An important embodimentof this invention is a surfactant composition comprising apolyoxyalkylene alkylamine containing at least about 2 moles of analkylene oxide group and any of a range of eye irritation reducingcompounds, such as sulfated polyoxyalkylene alkylphenol; alcoholsulfates; polyoxyalkylene alcohol sulfates; mono- and dialcoholphosphates; mono- and di-(polyoxyalkylene alcohol) phosphates; mono- anddi-(polyoxyalkylene alkylphenol) phosphates; polyoxyalkylene alkylphenolcarboxylates or polyoxyalkylene alcohol carboxylates, said eyeirritation reducing compounds containing up to about 60 moles of analkylene oxide group and alkyl and alcohol groups having from about 8 toabout 20 carbon atoms.

A glycol can be present in the surfactant composition in order toimprove the solubility of the surfactant composition. The glycol can beformed in situ during the preparation of the polyoxyalkylene alkylamine,or the glycol can be added to the amine or the surfactant composition.

Also the present invention contemplates pesticidal compositions,particularly herbicidal compositions, comprising a pesticide such as aherbicide and the aforedescribed surfactant composition. Thesecompositions are readily dispersible in water so as to prepare aqueouscompositions useful for the control of weeds, insects, fungi and thelike.

In accordance with a preferred embodiment of the present invention anaqueous solution is provided which comprises a herbicidally effectiveamount of a glyphosate herbicide, either in the acid or salt form, whoseherbicidal effectiveness is enhanced by the presence of a potentiatingeffective amount of a polyoxyalkylene alkylamine surfactant, and whoseeye irritancy caused by the presence of said alkylamine surfactant inthe solution is reduced by incorporating an eye irritation reducingamount of an anionic surfactant.

DETAILED DESCRIPTION OF THE INVENTION

The surfactant composition of the present invention comprise apolyoxyalkylene alkylamine having at least about 2 moles of an alkylenegroup, said surfactant composition having an eye irritancy lower thanthe eye irritancy of said polyoxyalkylene alkylamine.

One method for reducing the eye irritancy of the polyoxyalkylenealkylamine is to blend it with an effective amount of an eye irritationreducing compound. Examples of compounds useful for this purpose aresulfated polyoxyalkylene alkylphenol; alcohol sulfates; polyoxyalkylenealcohol sulfates; mono- and dialcohol phosphates; mono- anddi-(polyoxyalkylene alcohol) phosphates; mono- and di-(polyoxyalkylenealkylphenol) phosphates; polyoxyalkylene alkylphenol carboxylates orpolyoxyalkylene alcohol carboxylates, said eye irritation reducingcompounds containing up to about 60 moles of an alkylene oxide group andalkyl and alcohol groups having from about 8 to about 20 carbon atoms.

The present invention more specifically provides an aqueous or watersoluble composition comprising one or more salts of glyphosate in aherbicidally effective amount. The composition contains an aminesurfactant having the chemical structure ##STR1## wherein x is a numberfrom 7 to about 19, n₁ and n₂ are numbers independently selected from 1to about 30, the average sum of n₁ and n₂ is greater than 2, and R₁ andR₂ are C₂ -C₄ alkylene radicals. The amine surfactant is present in anamount sufficient to potentiate the glyphosate herbicidal activity. Alsopresent in the composition is an acidic compound having the chemicalstructure

    2. R.sub.3 --O--(R.sub.4 O).sub.m --X.sub.1

wherein R₃ is C₈ -C₂₀ alkyl or C₈ -C₂₀ alkylphenyl, R₄ is C₂ -C₄alkylene radical, m is a number from 0 to about 60, and X₁ is selectedfrom the group consisting of carboxylate, sulfate and phosphateradicals. The acidic compound is present in a sufficient amount toreduce the eye irritancy of the composition caused by the presence ofthe amine surfactant component to an acceptable level.

The present invention is directed to a surfactant composition comprisinga polyoxyalkylene C₈ -C₂₀ alkylamine surfactant having at least about2-moles of a C₂ -C₄ alkylene oxide group and reduced eye irritancy. Animportant embodiment of this invention is a surfactant compositioncomprising a polyoxyalkylene alkylamine surfactant containing at leastabout 2-4 moles of an alkylene oxide group and an effective amount of atleast one eye irritation reducing compound, such as sulfatedpolyoxyalkylene alkylphenol; alcohol sulfates; polyoxyalkylene alcoholsulfates; mono- and dialcohol phosphates; mono- and di-(polyoxyalkylenealcohol) phosphates; mono- and di-(polyoxyalkylene alkylphenol)phosphates; polyoxyalkylene alkylphenol carboxylates or polyoxyalkylenealcohol carboxylates, said eye irritation reducing compounds containingup to about 60 moles of a C₂ -C₄ alkylene oxide group and alkyl andalcohol groups having from about 8 to about 20 carbon atoms.

A glycol and/or polyalkylene glycol can be present in the surfactantcomposition in order to improve the water solubility of the surfactantcomposition and to suppress gelation of the surfactant composition inconcentrated form. The glycol or polyglycol can be formed in situ duringthe preparation of the polyoxyalkylene alkylamine, or the glycol orpolymeric glycol can be added to the amine or the surfactantcomposition.

Also, the present invention contemplates pesticidal compositions,particularly herbicidal compositions, comprising a pesticide, such as aherbicide and the aforedescribed surfactant composition having reducedeye irritancy. These compositions are readily dispersible or soluble inwater so as to prepare aqueous-based compositions useful for the controlof weeds, insects, fungi and the like.

In soaps, detergents and abrasives used for cleansing the skin onvarious portions of the body, anionic surfactants when used in suchcompositions are known to be adsorbed and thereby remain on the skinsurface to cause dryness and scaling of the epidermis, or skin chappingand roughness.

With the alkoxylated alkylamine surfactants known to cause eyeirritation in glyphosate-containing aqueous solutions and with the justdiscussed known drawbacks of anionic surfactants on skin, it issurprising and unexpected that the addition of an effective amount ofanionic surfactants to the aqueous solutions of alkoxylated alkylaminesurfactant would ameliorate the eye irritation thereof.

In accordance with the present invention, one method for reducing theeye irritancy of the polyoxyalkylene alkylamine is to blend such aminewith an effective amount of an eye irritation reducing compound.Examples of compounds useful for this purpose are sulfatedpolyoxyalkylene alkylphenol; alcohol sulfates and polyoxyalkylenealcohol sulfates; mono- and dialcohol phosphates; mono- anddi-(polyoxyalkylene alcohol) phosphates; mono- and di-(polyoxyalkylenealkylphenol) phosphates; polyoxyalkylene alkylphenol carboxylates orpolyoxyalkylene alcohol carboxylates, including mixtures thereof, saideye irritation reducing compounds containing up to about 60 moles of analkylene oxide group and alkyl and alcohol group having from about 8 toabout 20 carbon atoms.

In many but not all embodiments of the present invention, bothcomponents of the surfactant composition are polyoxyalkylenederivatives. Such materials are often referred to as an alkoxylatedproduct or an alkylene oxide product. Often these alkylene oxideproducts are mixtures of compounds containing different numbers ofalkylene oxide groups, of which one may predominate, being accompaniedby smaller proportions of products containing larger and smaller numbersof the alkylene oxide groups in the polyoxyalkylene portion of themolecule.

The polyoxyalkylene alkylamine surfactants are commercially availablematerials, being used as surfactants for the preparation of pesticidalcompositions, particularly herbicidal compositions wherein thealkylamine enhances the activity of the herbicide. Glyphosate is oneexample where the alkylamines notably enhance or potentiate theherbicidal activity thereof. These amine surfactants can be prepared byreacting under suitable conditions, preferably in the presence of acatalyst, an alkylene oxide, preferably ethylene and/or propylene oxidewith a long chain alkylamine, preferably an alkylamine containing fromabout 8 to about 20 carbon atoms. The oxyalkylated moiety can be arandom or block copolymer of ethylene and propylene oxide units. TheseC₈ -C₂₀ alkyl primary amines may be derived from naturally occurringproducts such as tallow, coconut, soybean or cotton seed oils and assuch are mixtures of amines. A preferred amine is tallowamine. Thepolyoxyalkylene derivatives thereof are prepared by reacting alkyleneoxide with the selected alkylamine at elevated temperatures andpressure. Procedures for carrying out these reactions are known to thoseskilled in the art.

A generalized structural representation of the polyoxyalkylenealkylamines is depicted as follows: ##STR2## wherein x is a number fromabout 7 to about 19; n₁ and n₂ are numbers independently selected from 1to about 30, and the average sum of n₁ and n₂ is 2 or greater and may beas high as 60; and R₁ and R₂ are independently selected from loweralkylene, having from about 2 to about 4 carbon atoms, preferably 2carbon atoms. The amount of alkylamine surfactant will be sufficient topotentiate the activity of the selected pesticide.

The amount of alkylene oxide used in the preparation of this componentof the surfactant composition varies with the ultimate use of thesurfactant composition. Normally, up to about 60 moles of oxyalkylenegroups in the polyoxyalkylene alkylamine are satisfactory, with fromabout 4 to about 20 moles being preferred, and from about 8 to about 13moles of oxyalkylene groups being most preferred.

Sulfated polyoxyalkylene alkylphenols can be prepared by firstalkoxylating an alkylphenol and then reacting the alkoxylatedalkylphenol with a suitable quantity of sulfur trioxide. One procedurefor such preparation is to contact a mixture of air and sulfur trioxidewith the selected alkoxylated alkylphenol in a falling film reactor.Other procedures that may be used include reactions with oleum or withchlorosulfonic acid. This reaction will cause the formation of sulfategroups as a terminal group on the alkoxylated portion of the moleculeand often some sulfonate groups substituted on the phenyl moiety. Thepreparation of the sulfated polyoxyalkylene alkylphenol can produceproduct having from 0 to 30 or more weight percent of the sulfatedpolyoxyalkylene alkylphenol having sulfonate groups on the phenylmoiety. For many purposes it is preferred that at least about 3 weightpercent of the sulfated polyoxyalkylene alkyl phenol be sulfonated.

In the acid form the sulfated polyoxyalkylene alkylphenols areinherently unstable under normal conditions. The adverse affects of suchinstability can be avoided by mixing the sulfated polyoxyalkylenealkylphenols shortly after their production with the alkylaminesurfactant. The mixing results in the formation of a stable salt of thetwo components. If it is desired to mix the two components at a timesignificantly later than the production of the sulfated polyoxyalkylenealkylphenol, a stable composition can be made and can be stored for sometime before mixing. For example, alkali metal salts and amine salts ofthe sulfated polyoxyalkylene alkylphenol surfactants are more stable ascompared to such surfactants in acid form.

A generalized structural representation of the predominant component ofthe sulfated polyoxyalkylene alkylphenol optionally containing ringsulfonation is as follows: ##STR3## wherein m is a number up to about60, preferably less than 10 and more preferably about 4, R is alkylenehaving from 2 to about 4 carbon atoms, preferably about 2, and R¹ isalkyl having about 8 to about 20 carbon atoms, preferably 9-15 carbonatoms. The amount of sulfated polyoxyalkylene alkylphenol compound inthe composition should be sufficient to reduce the eye irritation of thealkylamine surfactant. It is preferred that at least 3% of the sulfatedpolyoxyalkylene alkylphenol compound be ring sulfonated. The broken linein the above formula indicates that the ring sulfonation is optionaland, if sulfonated, the sulfonate substituent normally is in the meta orortho position with respect to R¹. Eye irritation reduction can beobtained without the compound having been ring sulfonated.

The amount of alkylene oxide used in the preparation of this componentof the surfactant composition varies with the ultimate use of thesurfactant composition. Normally, there can be up to about 30 or moremoles of alkylene oxide in the sulfated polyoxyalkylene alkylphenol. Forcertain agricultural applications it is preferred to have from abut 4 toabout 14 or more moles of the alkylene oxide units. For specific uses itis preferred that there be present less than 10 moles of alkylene oxidegroups and preferably about 4 moles of alkylene oxide groups, mostpreferably about 4 moles of ethylene oxide in the sulfatedpolyoxyalkylene alkylphenol having at least 3% sulfonation.

The alkyl group in the alkylphenol moiety can comprise from about 8 toabout 20 carbon atoms. A preferred alkyl is nonyl due to theavailability and properties of surfactants having this moiety. It shouldbe understood that for specific applications, alkylphenol moietiescontaining more or fewer carbon atoms can be used.

In order to obtain the desired results, of the total sulfatedpolyoxyalkylene alkylphenol preferably at least about 3 weight percenthave sulfonate substituents. The sulfonated component can comprise up to30 weight percent or more of the total alkylphenol. For certainapplications the sulfated polyoxyalkylene compounds of which about 15weight percent have sulfonate substituents can be effectively used inthe present surfactant composition.

Other eye irritant reducing compounds can also be used to reduce the eyeirritancy of the polyoxyalkylene alkylamines. Alcohol sulfates andpolyoxyalkylene alcohol sulfates having from about 8 to 18 carbon atomsand up to about 12 moles of alkoxyalkylene group are particularlyuseful. As with the sulfated polyoxyalkylene alkylphenol and thepolyoxyalkylene alkylamines, it is preferred that the alkylene oxidegroups in the polyalkylene alcohol sulfates be ethylene oxide groups.Oxyalkylene groups from 2 to about 4 carbon atoms are often used. Whilethere can be 30 or more moles of an oxyalkylene group in thepolyoxyalkylene alcohol sulfate, polyoxyalkylene alcohol sulfatepreferably contains about 3 moles of alkylene oxide groups, preferably 3moles of ethylene oxide groups.

Mono- and dialcohol phosphates; mono- and di-(polyoxyalkylene alcohol)phosphates; mono- and di-(polyoxyalkylene alkylphenol) phosphates;polyoxyalkylene alkylphenol carboxylates and polyoxyalkylene alcoholcarboxylates are additional eye irritant reducing compounds that can beused to reduce the eye irritancy of the polyoxyalkylene alkylamines.

These compounds can contain from about 8 to about 20 carbon atoms intheir alkyl and alcohol groups and up to about 30 moles of alkyleneoxide, preferably ethylene oxide, in each polyoxyalkylene alcohol orpolyoxyalkylene alkylphenol group. As with the sulfated polyoxyalkylenealkylphenol, it is preferred that the polyoxyalkylene alkylphenolphosphates and carboxylates be polyoxyethylene nonylphenol phosphatesand polyoxyalkylene nonylphenol carboxylates.

These carboxylates and phosphate components are available materialswhich can be readily prepared by methods known in the art. As oneexample of such a procedure, the phosphates can be obtained by reactinga suitable polyoxyalkylene alkylphenol with phosphorus pentoxide orpolyphosphoric acid. The selection of the exact components and theiramounts depends on the identification of the desired phosphate. Byvarying the components used in the preparation of the phosphate, it ispossible to maximize the presence of mono- or diester. Often thephosphates are mixtures of the mono- and diesters. The preference forthe mono- or diester of phosphoric acid depends upon variables such asthe ultimate use of the surfactant composition, the identify of thepesticide, the intended use of the pesticide composition and otherfactors. U.S. Pat. No. 4,313,847 describes the preparation of thephosphates.

The mono- and dialcohol phosphates, mono- and di-(polyoxyalkylenealcohol) phosphates and the mono- and dialcohol phosphates,(polyoxyalkylene alkylphenol) phosphates useful in accordance with thepresent invention are represented by the following general formula##STR4## wherein R¹ is C₈ -C₂₀ alkyl or C₈ -C₂₀ alkylphenyl; R is analkylene having from 2 to about 4 carbon atoms, usually ethylene orpropylene, m is zero or a number up to about 60, preferably less than 10and more preferably about 4, and R² is hydroxyl or the R¹ --O--(RO)_(m)-- radical, wherein R¹, R, and m are as just indicated. If R² ishydroxyl, then the compound is a monoester. If R² is a R¹ --O--(RO)_(m)-- radical, then the compound is a diester. Mixtures of monoesters anddiesters are also useful, together with the polyoxyalkylene alkylamines.

Certain of the eye irritant reducing components of the presentsurfactant compositions are commercial materials. For example,nonylphenol phosphate containing 4 moles of ethylene oxide, C₈ -C₁₀alcohol phosphates and sulfated nonylphenol containing 4 moles ofethylene oxide have been marketed by Witco Crop. under the names EMPHOSCS-121, EMPHOS PS-400, and WITCONATE D-51-29, respectively. (EMPHOS andWITCONATE are trademarks of Witco. Corp.)

More particularly, the phosphate mono-esters of polyoxyalkylenealkylphenol and the phosphates di-esters of the polyoxyalkylenealkylphenol useful for reducing the eye irritancy of the selectedpolyoxyalkylene alkylamine surfactant in accordance with the presentinvention, respectively, have the following chemical structures ##STR5##wherein m is zero or a number up to about 60, preferably 9-15, R is C₂-C₄ alkylene, preferably ethylene and R¹ is C₈ -C₂₀ alkyl or C₈ -C₂₀alkylphenyl. The amount of phosphate compound in the composition shouldbe sufficient to reduce the eye irritation of the polyoxyalkylenealkylamine surfactant. Mixtures of monoester and diester are alsouseful. Normally, the diester to the mono-ester is present in a weightratio of 5:95 to 50:50.

In general the surfactant composition comprises a major amount ofpolyoxyalkylene alkylamine component and an effective amount of theselected eye irritation reducing compound. The eye irritation reducingcompound is present in the surfactant composition in an effective amountsufficient to reduce the eye irritation properties of thepolyoxyalkylene alkylamine. When the eye irritation reducing compound isa sulfated polyoxyalkylene alkylphenol, preferred surfactantcompositions can contain from about 50 to about 95 weight percent,preferably about 80 to about 85 weight percent, of the polyoxyalkylenealkylamine and from about 5 to about 50 weight percent of the eyeirritation reducing component. The optimum amount of each component inthe surfactant blend depends on variables such as the identify of theeye irritation reducing compound, the identity of the pesticide, thetype of application of the pesticide composition, storage andtransportation of the surfactant and pesticide compositions, theconditions of use of the pesticidal compositions, etc. When a watersoluble salt of glyphosate is the pesticide and sulfated polyoxyalkylenealkylphenol is the eye irritation reducing component, it has been founddesirable to use a composition which comprises about 85 weight percentof the polyoxyalkylene alkylamine and about 15% by weight of thesulfated polyoxyalkylene alkylphenol. Other ratios may also be useful.

The surfactant composition of the present invention can contain optionalcomponents to improve the water solubility of the surfactant compositionand suppress gel formation. The need for such components will dependupon several factors, especially the identity of the surfactantscomprising the composition. Among compounds useful for improving thewater solubility of the surfactant composition are glycols andpolyglycols. Glycols are of particular use for this function due totheir solubility in water. The readily available glycols, ethyleneglycol, propylene glycol, polyethylene glycol and polypropylene glycolare satisfactory for this function although other glycols can also beused. Other organic compounds with high water solubility will also beuseful in certain instances. The antigelation additive preferably ispolyethylene glycol having an average molecular weight of about 200 toabout 1000.

While the glycol can be added to the surfactant composition with mixing,its use therein is independent of the method of its introduction intothe surfactant composition. Thus, for example, it can be introduced intothe surfactant composition with the polyoxyalkylene alkylaminecomponent. This is often a preferred method since the glycol and/orpolymeric glycol can be made during the manufacture of thepolyoxyalkylene alkylamine component as a byproduct of the alkoxylationreaction. Other procedures for obtaining and introducing the optionalglycol component can be used.

Most of the individual components discussed above are liquids at roomtemperatures. However, in the case of those materials containing a largepolyoxyalkylene chain, some of the materials may be waxy at roomtemperature and if this is the case, the materials can be heated toliquefy the same prior to mixing. The surfactant compositions of thepresent invention can be prepared by blending the components in aconventional manner. Any suitable equipment, such as conventional mixer,may be used. The order of adding the materials to the compositiongenerally is not critical and thus they may be blended in any convenientorder. As mentioned above, the amounts of the individual componentsutilized can be varied somewhat depending upon a variety of factors,particularly the ultimate application of the composition.

Surfactant compositions of the present invention are especially usefulin the preparation of pesticidal compositions designed to be deliveredby spraying, particularly sprayable herbicidal compositions. The term"pesticide" includes chemicals and microbial agents used as activeingredients of products for control of crop and lawn pests and diseases,animal ectoparasites, and other pests in public health. The term alsoincludes pant growth regulators, pest repellents, synergists, herbicidesafeners (which reduce the phytotoxicity of herbicides to crop plants)and preservatives, the delivery of which to the target may expose dermaland especially ocular tissue to the pesticide. Such exposure can ariseby drift of the pesticide from the delivery means to the personperforming the application of the pesticide or being present in thevicinity of an application.

In general, a herbicidal composition known as a concentrate is firstprepared. This composition in essence contains a herbicide and asurfactant mixture. Often it includes a minor amount of solvent, such aswater. Alternatively, the concentrate composition may be in dry formwith or without an inert solid carrier, for example, as a water solubleor water dispensible granular formulation. The ratio of herbicide tosurfactant will depend on many factors, including but not limited to theidentity of the components and the ultimate use. Usually the surfactantwill comprise from about 5 to about 25 weight percent of thiscomposition. The concentrate can then be diluted with water to form anaqueous herbicidal composition ready for use by spraying. The presentherbicidal compositions are not limited to a particular herbicide ormixture of herbicides. They may be used with a variety of pesticides,including but not limited to herbicides in any of their water solublesalt forms. Among such herbicides are glyphosate and acifluorfen(5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoic acid),chloramben (3-amino-2,5-dichlorobenzoic acid), 2,4-D((2,4-dichlorophenoxy) acetic acid), endothal(7-oxabicyclo(2.2.1)heptane-2,3-dicarboxylic acid), mecoprop(2-(2-methyl-4-chlorophenoxy) propionic acid), picloram(4-amino-3,5,6-trichloropyridine-2-carboxylic acid),2,4,5-T((2,4,5-trichlorophenoxy)acetic acid), benzac(2,3,6-trichlorobenzoic acid), dicamba (3,6-dichloro-o-anisic acid),MCPA (4-chloro-o-tolyloxyacetic acid), dalapon (2,2-dichloropropionicacid), dichlorprop (2-(2,4-dichlorophenoxy)propionic acid), MCPB(4-(4-chloro-o-tolyoxy)butyric acid), bialphos(L-2-amino-4-((hydroxy)(methyl) phosphinoyl)butyryl-L-alanyl-L-alanine), glufosinate((3-amino-3-carboxypropyl)methylphosphinate), imazethapyr(2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2yl]-5-ethyl-3-pyridinecarboxylicacid), imazaquin(2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-ozo-1H-imidazol-2-yl]-3-quinolinecarboxylicacid), mixtures thereof and the like. Preferred results, however, areobtained with the herbicide glyphosate whose activity is derived fromN-phosphonomethylglycine. Glyphosate is normally formulated from watersoluble salts thereof. U.S. Pat. No. 3,853,530 discloses the use ofglyphosate and its derivatives as herbicides.

Since glyphosate in acid form has limited water solubility (about 1.2%)the water soluble salts of glyphosate are normally used for mostapplications. Among the water soluble salts of glyphosate are thetrimethylsulfonium salt, the ammonium salt, the isopropylamine salt, andthe alkali metal salts, such as sodium and potassium. These compoundsdue to their solubility in water are the agriculturally acceptableglyphosate-containing compounds generally used in commerce.

It is known to use mixtures of glyphosate and one or more of its watersoluble salts. Previously mentioned European Patent 290,416 disclosesthe use of such mixtures which have the advantage of a higherconcentration of glyphosate in the final product. However, the lowsolubility of the glyphosate in acid form limits the amount of it in thetotal composition. This amount will depend in general on the solubilityof the water soluble salt used in the combination.

The pesticidal compositions previously described can be diluted withwater to form an aqueous pesticidal composition which can be sprayed orotherwise applied to the desired area. Glyphosate-based herbicides areapplied to the foliage of the vegetation to be controlled.

The relative amounts of herbicide, water and surfactant in the aqueousherbicidal compositions of this invention will vary depending upon manyfactors including but not limited to the identity and properties of theherbicide, method of application, locus to which the herbicide isapplied, etc.

The weight ratio of glyphosate expressed as acid equivalent tosurfactant composition is normally in the range of 1:1 to 5:1.

Stable aqueous concentrate compositions of the present invention can bemade with glyphosate salts at a concentration from about 5% to about50%, preferably about 35% to about 45%, surfactant composition at aconcentration of about 5% to about 25%, preferably about 10% to about15%, and water making up the balance to 100%. Dry water soluble granular(WSG) or water dispersible granular (WDG) compositions of the presentinvention can be made with glyphosate salts at a concentration fromabout 10% to about 85%, preferably about 50% to about 80%, surfactantcomposition at a concentration of about 5% to about 30%, preferablyabout 10% to about 25, and optionally inert ingredients making up thebalance to 100%. All percentages above are understood as being byweight.

It is to be noted that in accordance with the preferred practice of thepresent invention, a multicomponent surfactant composition is provided.One component is a polyoxyalkylene alkylamine surfactant as definedabove. A second component present in an eye irritancy reducing amount isan anionic sulfated polyoxyalkylene alkylphenol surfactant having thefollowing chemical structure which preferably contains a minor amount ofring sulfonation. ##STR6## wherein R¹, R and m are defined as above. Inother words, of the total polyoxyalkylene alkylphenol in the surfactantcomposition the mole percent of phenol compound having a sulfonatesubstituent to phenol compound having no sulfonate substituent ispreferably in the range of 3-50. The amount of the second component isan amount sufficient to result in an effective reduction of tissueirritation due to the presence of the amine surfactant component in thesurfactant composition. The --SO₃ H substituent on the phenyl moiety andR¹ are normally separated by one ring carbon.

It is also to be noted that in accordance with another preferredpractice of the present invention, a multicomponent surfactantcomposition is provided wherein one component is a cationicpolyoxyalkylene alkylamine surfactant as defined above and wherein asecond component present in an eye irritation reducing amount is aphosphate ester having one or both of the following chemical structures:##STR7## wherein m is zero or a number up to about 60, preferably 9-15,R is C₂ -C₄ alkylene, preferably ethylene and R¹ is C₈ -C₂₀ or C₈ -C₂₀alkylphenyl.

The surfactant composition of the present invention is normally solublein water and thus can be used in a water based formulation or watersoluble dry formulation for delivering such as by spraying apesticidally effective amount of the selected pesticide to the point ofdesired application.

In one preferred embodiment of the present invention the surfactantcomposition comprised of the amine surfactant component and the sulfatedpolyoxyalkylene alkylphenol having sulfonate substituents in the phenylmoiety and/or phosphate ester as above defined can effectively be usedto formulate glyphosate. Glyphosate is the widely recognized common namefor N-phosphonomethylglycine, the biologically active entity of which isthe acid form and may be used in the form of an ester but is normallyused in the form of water soluble salts. Water soluble salts includeakali metal salts of glyphosate, and organic salts of glyphosateincluding onium salts such as ammonium, sulfonium and phosphonium saltsof glyphosate. The most preferred salts include ammonium,isopropylammonium and trimethylsulfonium salts of glyphosate.

The surfactant composition of the present invention, in addition to theamine surfactant component and the anionic eye irritation reducingsurfactant component, may contain about 1-10 weight percent polyalkyleneglycol, preferably polyethylene glycol (PEG) having a molecular weightof about 200-1000 to increase the water solubility of the two othercomponents. Instead of or in addition to the polyethylene glycol (PEG),one may include in the surfactant composition of the present inventionethylene glycol and propylene glycol to further increase the watersolubility of the amine surfactant component and the eye irritationreducing component, if desired.

These following examples represent compositions tested to demonstratethe unexpectedly mild eye irritation properties provided by the presentinvention. All compositions contained the monoisopropylamine salt ofglyphosate as the herbicide. Tables 1 and 2 contain the results of thesetests. The following test procedure was used in these experiments.

These examples were performed in accordance with Pesticidal AssessmentGuidelines, Subdividsion F, Hazard Evaluation: Human and DomesticAnimals, U.S. Environmental Protection Agency (EPA) Publication, EPA540/9-84-014, November, 1984. Studies were conducted in compliance withEPA Good Laboratory Practice Standards (Federal Register, Vol. 48, Nov.29, 1983).

Unless otherwise indicated in each of the following examples, an aqueoussolution of the isopropylamine salt of glyphosate containing 61.3 weightpercent of such glyphosate salt was used as the herbicidal component andis referred to as "glyphosate solution". A mixture of about 70 weightpercent polyoxyethylene tallowamine containing from about 8 to 13 molesof ethylene oxide groups and about 30 weight percent polyethylene glycol(MW=600) which may be abbreviated as PEG-600 was used as a component ofthe surfactant composition and is referred to as "ethoxylatedtallowamine" or abbreviated as "ETA".

All parts and percentages in the following examples are given on aweight to weight basis unless otherwise indicated.

Examples 1 and 2 are experiments performed with a glyphosate compositioncontaining ethoxylated tallowamine as its only surfactant component.

EXAMPLE 1

Example 1 was performed with a test material prepared by mixingglyphosate solution (69.3 grams), ethoxylated tallowamine (13.0 grams)and water (17.7 grams).

EXAMPLE 2

Example 2 was performed with a test material prepared by mixingglyphosate solution (69.3 grams), ethoxylated tallowamine (15.4 grams)and water (15.3 grams).

Examples 3-13 are experiments performed with a surfactant compositioncontaining ethoxylated tallowamine and a sulfated ethoxylatednonylphenol.

EXAMPLE 3

Example 3 was performed with a test material prepared by mixingglyphosate solution (69.3 grams), water (15.3 grams) and surfactantcomposition (15.4 grams) having a pH of 7.5 and containing ethoxylatedtallowamine (13.1 grams) and sulfated polyoxyethylene nonylphenol (2.2grams) having 4 moles of ethylene oxide groups and about 3 weightpercent sulfonate.

EXAMPLE 4

Example 4 was performed with a test material prepared by mixingglyphosate solution (69.3 grams); water (15.2 grams) and surfactantcomposition (15.4 grams) containing ethoxylated tallowamine (13.5 grams)and sulfated polyoxyethylene nonylphenol (1.9 grams) having 2 moles ofethylene oxide groups and about 6 weight percent sulfonate.

EXAMPLE 5

Example 5 was performed with a test material prepared by mixingglyphosate solution (69.3 grams), water (15.3 grams) and surfactantcomposition (15.4 grams) containing ethoxylated tallowamine (13.5 grams)and sulfated polyoxyethylene nonylphenol (1.9 grams) having 2 moles ofethylene oxide groups and about 15 weight percent sulfonate.

EXAMPLE 6

Example 6 was performed with a test material prepared by mixingglyphosate solution (2.94 grams), water (96.39) grams and surfactantcomposition (0.67 grams) containing JETCO ethoxylated tallowamine (0.57grams) and sulfated polyoxyethylene nonylphenol (0.10 grams) having 4moles of ethylene oxide groups and about 6 weight percent sulfonate.

EXAMPLE 7

Example 7 was prepared by mixing glyphosate solution (2.94 grams), water(96.39 grams) and surfactant composition (0.67 grams) containing ARMAKethoxylated tallowamine (0.57 grams) and sulfated polyoxyethylenenonylphenol (0.10 grams) having 4 moles of ethylene oxide groups andabout 6 weight percent sulfonate.

EXAMPLE 8

Example 8 was prepared by mixing glyphosate solution (69.3 grams), water(15.3 grams) and surfactant composition (15.4 grams) containingethoxylated tallowamine (13.1 grams) and sulfated polyoxyethylenenonylphenol (2.3 grams) having 4 moles of ethylene oxide groups andabout 6 weight percent sulfonate.

EXAMPLE 9

Example 9 was prepared by mixing glyphosate solution (69.3 grams), water(15.3 grams) and surfactant composition (15.4 grams) containingethoxylated tallowamine (13.1 grams) and sulfated polyoxyethylenenonylphenol (2.3 grams) having 4 moles of ethylene oxide groups andabout 13 weight percent sulfonate.

EXAMPLE 10

Example 10 was prepared by mixing a glyphosate solution (69.3 grams),water (15.3 grams) and a surfactant composition (15.4 grams) having a pHof 6.5 containing ethoxylated tallowamine (13.1 grams) and sulfatedpolyoxyethylene nonylphenol (2.3 grams) having 4 moles of ethylene oxideand about 85 weight percent sulfonate.

EXAMPLE 11

Example 11 was prepared by mixing a glyphosate solution (69.3 grams),water (15.3 grams) and a surfactant composition (15.4 grams) having a pHof 7.1 containing ethoxylated tallowamine (13.8 grams) sulfatedpolyoxyethylene nonylphenol (1.5 grams) having with 4 moles of ethyleneoxide and about 85 weight percent sulfonate.

EXAMPLE 12

Example 12 was prepared by mixing a glyphosate solution (69.3 grams),water (15.3 grams) and a surfactant composition (15.4 grams) having a pHof 7 containing ethoxylated tallowamine (13.1 grams) and sulfatedpolyoxyethylene nonylphenol (2.3 grams) having 10 moles of ethyleneoxide groups and about 6 weight percent sulfonate.

EXAMPLE 13

Example 13 was prepared by mixing a glyphosate solution (69.3 grams),water (15.3 grams) and a surfactant composition (15.4 grams) containingethoxylated tallowamine (11.9 grams) and sulfated polyoxyethylenenonylphenol (3.5 grams) having 10 moles of ethylene oxide groups andabout 6 weight percent sulfonate.

Examples 14 and 15 are experiments performed with a surfactantcomposition containing ethoxylated tallowamine and an alcohol sulfate.

EXAMPLE 14

Example 14 was prepared by mixing a glyphosate solution (69.3 grams),water (15.3 grams) and a surfactant composition (15.4 grams) containingethoxylated tallowamine (13.1 grams) and alcohol sulfate (2.3 grams)from a mixture of alcohols having from 8 to 10 straight chain carbonatoms.

EXAMPLE 15

Example 15 was prepared by mixing a glyphosate solution (69.3 grams),water (15.3 grams) and a surfactant composition (15.4 grams) containingethoxylated tallowamine (13.9 grams) and alcohol sulfate (1.5 grams)from a mixture of alcohols having from 8 to 10 carbon atoms.

In Tables 1 and 2 below data are provided showing the average eyeirritation of six rabbits exposed in individual tests to each of thecompositions of Examples 1-15 using the EPA test referenced above. Thedata in Table 1 were obtained where the composition was not washed outof the eyes. The data in Table 2 were obtained where the composition waswashed out of the rabbits' eyes after being applied to the eyes.Observations are made after 1 hour, 1 day, 2 days, etc. after initialinstillation. The average score is an indication of the eye irritationpotential of the composition under test.

                  TABLE 1                                                         ______________________________________                                        Average Irritation Scores (Non-Washed Eyes)                                   EX-            DAYS AFTER TREATMENT                                           AMPLE  1 hr   1      2    3    4    7    10  14  17  21                       ______________________________________                                        1      18.0   15.2   19.0 14.0 11.8 10.5 7.0 5.3 3.8 4.0                      2      20.7   19.3   17.2 15.3 12.3 4.7  6.3 6.5 5   3.5                      3      17.2   10.2   10.8 9.2  7.6  6.4  6.4 9.5 6.5 9                        4      15.3   21.2   13   9.2  8.2  5.3  4.3 4.5 5   3.2                      5      19     19.2   10.2 6    4.3  1.7  0.7 0.7 0.7 0.3                      6      4      2.3    1    0    0    --    -- --  --  --                       7      4.7    1.7    1    0    --   --   --  --  --  --                       8      12     12.7   8.6  5.2  3.6  0.8  0   --  --  --                       9      12     14.8   8.2  5.3  4.7  1.7  0.3 0   --  --                       10     17.2   8.2    6.5  4.8  3.3  1.7  0.7 0   --  --                       11     17.3   10.5   7    4.7  3.7  1.3  0.7 0   --  --                       12     15.8   13.8   9.7  8.3  5    3    2.7 1   0.3 0.3                      13     17.7   12.3   10   6    4    2.3  2.3 2.2 0   --                       14     12.7   2      0.7  0    --   --   --  --  --  --                       15     17.7   14.7   8.3  6.5  7.7  2.3  3.2 1.3 1.3 1.3                      ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Average Irritation Scores (Washed Eyes)                                                DAYS AFTER TREATMENT                                                 EXAMPLE 1 hr   1      2    3    4    7   10  14  17  21                       ______________________________________                                        1       17.3   13.3   6.0  3.3  3.3  2.0 1.3 0.7 0.7 0.7                      2       21     17.7   13.7 11.3 8.7  4.7 4   8.7 5   3.7                      3       15     10     7.3  6    5.5  1.3 0.7 0   --   --                      4       15     6.7    4    2.7  2    0   --  --  --                           5       19.7   11.7   6.7  6    4.7  3.3 2   1.3 0.7 0.7                      6       11.7   4      1.3  0.7  0    --  --  --  --  --                       7       5.3    1.3    1.3  0    --   --  --  --  --  --                       8       15     6.7    5.3  4.7  3.3  0.7 0   --  --  --                       9       12.7   12.7   9.3  6    4    2   0   --  --  --                       10      13.3   7.3    4.7  2.7  1.3  0.7 0   --  --  --                       11      12.7   6.7    4.7  4.7  3.3  2   0   --  --  --                       12      19.7   14     10   8    9    5.3 4   3.7 2   0                        13      19     11     7.7  4.7  3.3  2.1 1.3 0   --  --                       14      9.7    0.7    0    0    --   --  --  --  --                           15      16.3   9.3    6.0  4.0  2.0  0.7 0   --  --  --                       ______________________________________                                    

The test materials were rated and classified into toxicity categories bythe following system:

    ______________________________________                                                    Maximum                                                           Rating      Average Score                                                                              Definition                                           ______________________________________                                        Non-Irritating                                                                            0.0-0.5      To maintain this category,                                                    all scores at the 24-hour                                                     reading must be zero;                                                         otherwise increase                                                            category one level.                                  Practically Non-                                                                          Greater than 0.5-                                                                          To maintain this category,                           Irritating  2.5          all scores at the 24-hour                                                     reading must be zero;                                                         otherwise increase                                                            category one level.                                  Mimimally Irritating                                                                      Greater than 2.5-                                                                          To maintain this category,                                       15.0         all scores at the 72-hour                                                     reading must be zero;                                                         otherwise increase                                                            category one level.                                  Mildly Irritating                                                                         Greater than 15.0-                                                                         To maintain this category,                                       25.0         scores at the 7-day reading                                                   must be zero; otherwise                                                       increase category one                                                         level.                                               Moderately Irritating                                                                     Greater than 25.0-                                                                         To maintain this category,                                       50.0         scores at the 7-day reading                                                   must be less than or equal                                                    to 10 for 60% or more of                                                      the animals. Also, the 7-                                                     day mean score must be                                                        less than or equal to 20.                                                     If the 7-day mean score is                                                    less than or equal to 20,                                                     but less than 60% of the                                                      animals show scores less                                                      than 10, then no animai                                                       among those showing                                                           scores greater than 10 can                                                    exceed a score of 30 if                                                       category is to be                                                             maintained; otherwise                                                         increase category one                                                         level.                                               Severely Irritating                                                                       Greater than 50.0-                                                                         To maintain this category,                                       80.0         scores at the 7-day reading                                                   must be less than or equal                                                    to 30 for 60% or more of                                                      the animais. Also, the 7-                                                     day mean score must be                                                        less than or equal to 40.                                                     If the 7-day mean score is                                                    less than or equal to 40,                                                     but less than 60% of the                                                      animals show scores less                                                      than or equal to 30, then                                                     no animal among those                                                         showing scores greater                                                        than 30 can exceed a score                                                    of 60 if category is to be                                                    maintained; otherwise                                                         increase category one                                                         level.                                               Extremely Irritating                                                                      Greater than 80.0-                                                            110.0                                                             ______________________________________                                    

The category of the test material is not to be increased more than onelevel above its maximum average score.

CLASSIFICATION OF TEST MATERIAL INTO TOXICITY CATEGORIES

    ______________________________________                                        Category                                                                              Criteria                                                              ______________________________________                                        I       Corrosive (irreversible destruction of ocular tissue) or                      corneal involvement or conjunctival irritation persisting                     through Day 21.                                                       II      Corneal involvement or conjunctival irritation clearing in                    8-21 days.                                                            III     Corneal involvement or conjunctival irritation clearing 7                     days or less.                                                         IV      Minimal effects clearing in less than 24 hours.                       ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Test Ratings (Non-Washed Eyes)                                                Example    Rating        Toxicity Category                                    ______________________________________                                        1          Moderately Irritating                                                                       I                                                    2          Moderately Irritating                                                                       I                                                    3          Moderately Irritating                                                                       I                                                    4          Moderately Irritating                                                                       I                                                    5          Mildly Irritating                                                                           I                                                    6          Minimally Irritating                                                                        III                                                  7          Minimally Irritating                                                                        III                                                  8          Mildly Irritating                                                                           II                                                   9          Mildly Irritating                                                                           II                                                   10         Moderately Irritating                                                                       II                                                   11         Moderately Irritating                                                                       II                                                   12         Moderately Irritating                                                                       I                                                    13         Moderately Irritating                                                                       II                                                   14         Minimally Irritating                                                                        III                                                  15         Moderately Irritating                                                                       I                                                    ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        Test Ratings (Washed Eyes)                                                    Example    Rating        Toxicity Category                                    ______________________________________                                        1          Moderately Irritating                                                                       I                                                    2          Moderately Irritating                                                                       I                                                    3          Mildly Irritating                                                                           III                                                  4          Mildly Irritating                                                                           III                                                  5          Mildly Irritating                                                                           I                                                    6          Moderately Irritating                                                                       III                                                  7          Minimally Irritating                                                                        III                                                  8          Mildly Irritating                                                                           III                                                  9          Mildly Irritating                                                                           II                                                   10         Mildly Irritating                                                                           II                                                   11         Mildly Irritating                                                                           II                                                   12         Moderately Irritating                                                                       I                                                    13         Moderately Irritating                                                                       II                                                   14         Minimally Irritating                                                                        III                                                  15         Moderately Irritating                                                                       II                                                   ______________________________________                                    

Each of the test materials within the scope of the present invention,i.e. Examples 3-15 demonstrate a reduction of the eye irritancy bycomparison with compositions of the prior art containing ethoxylatedtallowamine but no eye irritation reducing compound, ie. Examples 1 and2.

In order to determine the efficacy of herbicidal compositions containinga sulfated polyoxyethylene nonylphenol surfactant as an eye irritationreducing agent, the following tests were performed using theisopropylamine salt of glyphosate as the herbicide.

EXAMPLE 16

In this experiment, herbicidal compositions of the present inventionwere compared with a standard glyphosate composition for herbicidalefficacy. In the tests, material A (standard) was the glyphosatecomposition containing 15.47 weight percent ethoxylated tallowamine.Materials B, C and D were glyphosate compositions comprising asurfactant composition containing ethoxylated tallowamine (13.1 grams)and sulfated polyoxyethylene nonylphenol (2.3 grams) having 4 moles ofethylene oxide and about 13 weight percent sulfonate as described inExample 9. Material B contained 15.49 weight percent of totalsurfactant, Material C contained 12.57 weight percent of totalsurfactant and Material D contained 10.0 weight percent of totalsurfactant.

The test materials were then diluted with water into 0.5, 1.0, 2.0 and4.0 weight percent glyphosate aqueous solutions and sprayed onto a testfield containing rhizome Johnsongrass. The test plots were evaluated 7and 14 days after treatment. Percent control of the Johnsongrass isshown in Table 5.

                  TABLE 5                                                         ______________________________________                                        Percent Control                                                               0.5%         1.0%      2.0%       4.0%                                        Test  7       14     7    14    7    14   7     14                            Material                                                                            days    days   days days  days days days  days                          ______________________________________                                        A     42      82     62   99    67   100  88    100                           B     57      90     75   99    68    99  88    100                           C     42      97     70   99    73   100  88    100                           D     47      95     58   99    73    99  83    100                           ______________________________________                                         An untreated check plot showed 0% control of the plants.                 

EXAMPLE 17

The test materials described in Example 17 were also applied to a testplot containing as its primary vegetation volunteer wheat, yellowfoxtail and prickly sida. Also present in the plots were scatteredplants of seedling Johnsongrass, velvetleaf and common lambsquarter.

All plots were evaluated 7 and 14 days after treatment. Percent controlis shown in Tables 6 and 7.

                  TABLE 6                                                         ______________________________________                                        Percent Control                                                               (7 days after treatment - Average of 3 Plots)                                 Test Rate    Volun-  Yellow      John-       Lambs-                           Mat- (Pints/ teer    Fox-  Prickly                                                                             son-  Velvet-                                                                             Quar-                            erial                                                                              Acre    Wheat   tail  Sida  Grass*                                                                              Leaf* ter*                             ______________________________________                                        A    1.0     87      93    72    80    60    --                                    1.5     95      95    82    90    85    --                                    2.0     97      98    88    95    --    95                               B    1.0     92      93    73    85    --    --                                    1.5     98      97    88    87.5  --    95                                    2.0     100     100   95    95    90    --                               C    1.0     90      92    82    85    65    --                                    1.5     97      97    93    92.5  80    --                                    2.0     98      98    93    95      92.5                                                                              90                               D    1.0     93      93    90    --    60    --                                    1.5     98      97    90    90    90    --                                    2.0     100     98    93    95    90    --                               ______________________________________                                         *Insufficient Johnsongrass, Velvetleaf and Lambsquarter plants for            complete evaluation.                                                     

                  TABLE 7                                                         ______________________________________                                        Percent Control                                                               (14 days after treatment - Average of 3 Plots)                                Test Rate    Volun-  Yellow      John-       Lambs-                           Mat- (Pints/ teer    Fox-  Prickly                                                                             son-  Velvet-                                                                             Quar-                            erial                                                                              Acre    Wheat   tail  Sida  Grass*                                                                              Leaf* ter*                             ______________________________________                                        A    1.0     100     100    95    95   95    --                                    1.5     100     100   100   100   100   --                                    2.0     100     100   100   100   --    100                              B    1.0     100     100    98   100   --    --                                    1.5     100     100   100   100   --     95                                   2.0     100     100   100   100   100   --                               C    1.0     100     100    97   100    80   --                                    1.5     100     100    98   100    95   --                                    2.0     100     100   100   100   100   100                              D    1.0     100     100    98   --     80   --                                    1.5     100     100   100   100   100   --                                    2.0     100     100   100   100    95   --                               ______________________________________                                         *Insufficient Johnsongrass, Velvetleaf and Lambsquarter plants for            complete evaluation.                                                     

The untreated check plot had 0% control of all test plants.

The foregoing herbicidal test results demonstrate that herbicidalcompositions containing the surfactant compositions of the presentinvention maintain or increase the herbicidal activity of herbicidalcompositions containing an alkoxylated alkylamine as the only surfactantand provide reduced eye irritation.

In each of the following Examples 18-35, an aqueous solution of theisopropylamine salt of glyphosate containing 62.5 weight percent of suchglyphosate salt was used as the herbicidal component and is referred toas "glyphosate solution".

EXAMPLE 18

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams) and surfactantcomposition (15.4 grams) to form an aqueous solution. The surfactantcomposition of this example consisted of 1) ethoxylated tallowamine(13.1 grams) containing about 16-17 moles of ethylene oxide units andabout 2-5 weight percent polyethylene glycol (MW=600), and 2) amonohydric phosphate (2.3 grams) from a mixture of alcohols having from8 to 10 straight chain carbon atoms, no ethylene oxide units, and aphosphomonoester to phosphodiester ratio of 65.5:19.8.

EXAMPLE 19

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams) and surfactantcomposition (15.4 grams) to form an aqueous solution. The surfactantcomposition of this example consisted of 1) ethoxylated tallowamine(12.3 grams) containing from about 16-17 moles of ethylene oxide unitsand about 2-5 weight percent polyethylene glycol (MW=600), and 2) themonohydric phosphate of Example 18 (3.1 grams).

EXAMPLE 20

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams) and surfactantcomposition (15.4 grams) to form an aqueous solution. The surfactantcomposition consisted of 1) ethoxylated tallowamine (13.1 grams)containing about 16-17 moles of ethylene oxide groups and about 2-5weight percent polyethylene glycol (MW=600), and 2) a phosphatedpolyoxyethylene nonylphenol (2.3 grams) having 4 moles of ethylene oxidegroups and a phosphomonoester to phosphodiester ratio of 76.4:14.1.

EXAMPLE 21

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams), and surfactantcomposition (15.4 grams) to form an aqueous solution. The surfactantcomposition consisted of 1) ethoxylated tallowamine (11.5 grams)containing about 16-17 moles of ethylene oxide groups and about 2-5weight percent polyethylene glycol (MW=600), and 2) the phosphatedpolyoxyethylene nonylphenol of Example 20 (3.9 grams).

EXAMPLE 22

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams), and surfactantcomposition (15.4 grams) to form an aqueous solution. The surfactantcomposition consisted of 1) ethoxylated tallowamine (12.3 grams)containing about 8-13 moles of ethylene oxide groups and about 30 weightpercent polyethylene glycol (MW=600), and 2) the phosphatedpolyoxyethylene nonylphenol of Example 20 (3.1 grams).

EXAMPLE 23

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams), and surfactantcomposition (15.4 grams) to form an aqueous solution. The surfactantcomposition consisted of 1) ethoxylated tallowamine (13.1 grams)containing about 8-13 moles of ethylene oxide groups and about 30 weightpercent polyethylene glycol (MW=600), and 2) the monohydric phosphate ofExample 18 (2.3 grams).

EXAMPLE 24

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams), polyethyleneglycol (MW=400) (5.0 grams), and surfactant composition (10.4 grams) toform an aqueous solution. The surfactant composition consisted of 1)ethoxylated tallowamine (6.2 grams) containing about 8-13 moles ofethylene oxide groups and about 30 weight percent polyethylene glycol(MW=600), and 2) a phosphated polyoxyethylene nonylphenol (4.2 grams)having 4 moles of ethylene oxide groups and a phosphomonoester tophosphodiester ratio of 73.6:11.8.

EXAMPLE 25

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams) and surfactantcomposition (15.4 grams) to form an aqueous solution. The surfactantcomposition consisted of 1) ethoxylated tallowamine (11.6 grams)containing about 8-13 moles of ethylene oxide groups and about 30 weightpercent polyethylene glycol (MW=600), and 2) a monohydric phosphate of(3.8 grams) from a mixture of alcohols having from 8 to 10 straightchain carbon atoms, no ethylene oxide units, and a phosphomonoester tophosphodiester ratio of 64.3:20.7.

EXAMPLE 26

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams), and surfactantcomposition (15.4 grams) to form an aqueous solution. The surfactantcomposition consisted of 1) ethoxylated tallowamine (9.2 grams)containing about 16-17 moles of ethylene oxide groups and about 2-5weight percent polyethylene glycol (MW=600), and 2) the phosphatedpolyoxyethylene nonylphenol of Example 24 (6.2 grams).

EXAMPLE 27

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams), polyethyleneglycol (MW=400) (5.0 grams), and surfactant composition (10.4 grams) toform an aqueous solution. The surfactant composition consisted of 1)ethoxylated tallowamine (7.8 grams) containing from about 16-17 moles ofethylene oxide groups and about 2-5 weight percent polyethylene glycol(MW=600), and 2) the monohydric phosphate of Example 25 (2.6 grams).

EXAMPLE 28

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams), polyethyleneglycol (MW=400) (5.0 grams), and surfactant composition (10.4 grams) toform an aqueous solution. The surfactant composition consisted of 1)ethoxylated tallowamine (6.2 grams) containing about 8-13 moles ofethylene oxide groups and about 30 weight percent polyethylene glycol(MW=600), and 2) the phosphated polyoxyethylene nonylphenol of Example24 (4.2 grams).

EXAMPLE 29

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams), and surfactantcomposition (15.4 grams) to form an aqueous solution. The surfactantcomposition consisted of 1) ethoxylated tallowamine (11.6 grams)containing about 8-13 moles of ethylene oxide groups and about 30 weightpercent polyethylene glycol (MW=600), and 2) the monohydric phosphate ofExample 25 (3.8 grams).

EXAMPLE 30

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams), and surfactantcomposition (15.4 grams) to form an aqueous solution. The surfactantcomposition consisted of 1) ethoxylated tallowamine (9.2 grams)containing about 15 moles of ethylene oxide groups and about 2-5 weightpercent polyethylene glycol (MW=600), and 2) the phosphatedpolyoxyethylene nonylphenol of Example 24 (6.2 grams).

EXAMPLE 31

In this example a herbicidal composition was prepared by mixingglyphosate solution (68.5 grams), water (16.1 grams), polyethyleneglycol (MW=400) (5.0 grams), and surfactant composition (10.4 grams) toform an aqueous solution. The surfactant composition consisted of 1)ethoxylated tallowamine (7.8 grams) containing about 15 moles ofethylene oxide groups and about 2-5 weight percent polyethylene glycol(MW=600), and 2) the monohydric phosphate of Example 25 (2.6 grams).

In Table 8 which follows data are provided showing the average eyeirritation scores of six rabbits exposed in individual tests withoutwashing to each of the compositions in Examples 18-31.

                                      TABLE 8                                     __________________________________________________________________________    Average Irritation Scores (Non-Washed Eyes)                                             DAYS AFTER TREATMENT                                                EXAMPLE                                                                              1 hr                                                                             1  2  3  4  7  10 14 17 21                                          __________________________________________________________________________    18     11.3                                                                             12 12.2                                                                             17.3                                                                             14.8                                                                             16.3                                                                             15.8                                                                             16.3                                                                             15.3                                                                             7.8                                         19     9.3                                                                              9.7                                                                              13.7                                                                             16.0                                                                             16.8                                                                             19.7                                                                             21.8                                                                             17.7                                                                             19.8                                                                             13.3                                        20     8.3                                                                              9.3                                                                              13.5                                                                             10.7                                                                             8.6                                                                              11.8                                                                             12.8                                                                             10.5                                                                             9.5                                                                              6.3                                         21     9.3                                                                              10.8                                                                             13.7                                                                             13.8                                                                             13.5                                                                             15.8                                                                             13.2                                                                             11.5                                                                             8.0                                                                              5.0                                         22     18.5                                                                             14.8                                                                             11.3                                                                             7.3                                                                              6.5                                                                              4.3                                                                              2.8                                                                              1.8                                                                              1.5                                                                              1.5                                         23     20.8                                                                             19.0                                                                             16.2                                                                             19.3                                                                             12.7                                                                             8.3                                                                              6.3                                                                              5.0                                                                              4.7                                                                              8.0                                         24     11.0                                                                             6.7                                                                              4.7                                                                              2.3                                                                              0.3                                                                              0.3                                                                              0  --  --                                                                              --                                          25     14.0                                                                             10.0                                                                             8.5                                                                              4.3                                                                              2.0                                                                              1.3                                                                              0  -- -- --                                          26     11.3                                                                             11.2                                                                             9.2                                                                              8.8                                                                              8.2                                                                              2.2                                                                              1.0                                                                              0  -- --                                          27     12.8                                                                             11.7                                                                             10.3                                                                             8.0                                                                              7.3                                                                              3.8                                                                              3.2                                                                              2.0                                                                              2.3                                                                              2.0                                         28     11.7                                                                             7.3                                                                              5.0                                                                              3.0                                                                              3.0                                                                              1.0                                                                              0  -- -- --                                          29     14.8                                                                             12.5                                                                             11.3                                                                             9.0                                                                              7.2                                                                              1.5                                                                              0  -- -- --                                          30     11.5                                                                             9.8                                                                              4.7                                                                              3.0                                                                              2.7                                                                              0.7                                                                              0  -- -- --                                          31     12.2                                                                             11.3                                                                             9.8                                                                              7.5                                                                              6.3                                                                              2.2                                                                              1.2                                                                              1.2                                                                              1.2                                                                              0                                           __________________________________________________________________________

EXAMPLE 32

In this example of prior art a herbicidal composition was prepared bymixing glyphosate solution (68.5 grams), water (21.5 grams), andsurfactant composition (10.0 grams) to form an aqueous solution. Thesurfactant composition consisted of 1) ethoxylated tallowamine (7.2grams) containing about 15 moles of ethylene oxide groups, and 2)additional polyethylene glycol (MW=600), ethylene glycol, and water tototal 2.8 grams. The resulting composition was tested for eye irritationas above and gave results placing it in Toxicity Category I.

EXAMPLE 33

In this example of the present invention a herbicidal composition wasprepared by mixing glyphosate solution (68.5 grams), water (18.2 grams),and surfactant composition (13.3 grams) to form an aqueous solution. Thesurfactant composition consisted of 1) ethoxylated tallowamine (7.2grams) containing about 15 moles of ethylene oxide groups, 2) thephosphated polyoxyethylene nonylphenol of Example 20 (3.0 grams) and 3)additional polyethylene glycol (MW=600) and dipropylene glycol to total3.1 grams. The resulting composition was tested for eye irritation asabove and gave results placing it in Toxicity Category III.

EXAMPLE 34

In this example of prior art a herbicidal composition was prepared bymixing glyphosate solution (68.5 grams), water (16.1 grams), andsurfactant composition (15.4 grams) to form an aqueous solution. Thesurfactant composition consisted of 1) ethoxylated tallowamine (11.0grams) containing about 15 moles of ethylene oxide groups, and 2)additional polyethylene glycol (MW=600), ethylene glycol, and water tototal 4.4 grams. The resulting composition was tested for eye irritationas above and gave results placing it in Toxicity Category I.

EXAMPLE 35

In this example of the present invention a herbicidal composition wasprepared by mixing glyphosate solution (68.5 grams), water (2.5 grams),and surfactant composition (29.0 grams) to form an aqueous solution. Thesurfactant composition consisted of 1) ethoxylated tallowamine (11.0grams) containing about 15 moles of ethylene oxide groups, 2) thephosphated polyoxyethylene nonylphenol of Example 20 (3.6 grams), and 3)additional polyethylene glycol 600), propylene glycol, and dipropyleneglycol to total 14.4 grams. The resulting composition was tested for eyeirritation as above and gave results placing it in Toxicity Category II.

It should be understood that embodiments of the present invention havebeen described as merely illustrative of a few of the applications ofthe principles of the present invention. Numerous modifications may bemade by those skill in the art without departing from the spirit andscope of the invention.

What is claimed is:
 1. An aqueous concentrate herbicidal compositioncomprising(a) about 5% to about 50% by weight of a water soluble salt ofglyphosate; (b) an amine surfactant component consisting of (i) one ormore compounds having the chemical structure ##STR8## wherein x is anumber from 7 to about 19, n₁ and n₂ are numbers independently selectedfrom 1 to about 30, the average sum of n₁ and n₂ is 2 or greater, and R₁and R₂ are C₂ -C₄ alkylene radicals; and (ii) one or more glycolsselected from ethylene glycol, propylene glycol, polyethylene glycol andpolypropylene glycol in an amount of zero to about 30% by weight of theamine surfactant component; said amine surfactant component being in anamount sufficient to cause unacceptable eye irritation; (c) an effectiveeye irritation reducing amount of a phosphate surfactant componentconsisting of a phosphate monoester or mixture of phosphate monoestershaving the chemical structure ##STR9## where R⁷ is C₈ -C₂₀ alkyl or C₈-C₂₀ alkylphenyl, R is C₂ -C₄ alkylene, and m is a number from zero toabout 60; alone or in combination with a phosphate diester or mixture ofphosphate diesters having the chemical structure ##STR10## where R⁷, Rand m are as defined immediately above; and (d) water in an amountsufficient to provide a stable aqueous solution of the salt ofglyphosate in presence of the amine and phosphate surfactant components.2. The composition of claim 1 wherein the water soluble salt ofglyphosate is selected from the trimethylsulfonium, ammonium,isopropylamine, sodium and potassium salts.
 3. The composition of claim1 wherein the water soluble salt of glyphosate is present in an amountof about 35% to about 45% by weight.
 4. The composition of claim 1wherein, in the amine surfactant component, R₁ and R₂ are each ethyleneand the average sum of n₁ and n₂ is about 4 to about
 20. 5. Thecomposition of claim 1 wherein the amine surfactant component comprisespolyoxyethylene tallowamine having about 8 to about 13 moles of ethyleneoxide.
 6. The composition of claim 1 wherein, in the phosphatesurfactant component, R¹ is nonylphenol and m is about
 4. 7. Thecomposition of claim 1 wherein the phosphate monoester or monoesters arepresent in an amount that exceeds the amount of the phosphate diester ordiesters.
 8. The composition of claim 1 wherein the amine surfactantcomponent and the phosphate surfactant component are present in a totalsurfactant amount of about 5% to about 25% by weight.
 9. The compositionof claim 1 wherein the amine surfactant component and the phosphatesurfactant component are present in a total surfactant amount such thatthe weight ratio of glyphosate, expressed as acid equivalent, to totalsurfactant is about 1:1 to about 5:1.
 10. The composition of claim 1wherein the weight ratio of the amine surfactant component to thephosphate surfactant component is about 60:40 to about 85:15.
 11. Thecomposition of claim 1 wherein the weight ratio of the amine surfactantcomponent to the phosphate surfactant component is about 70:30 to about85:15.
 12. The composition of claim 1 wherein the weight ratio of theamine surfactant component to the phosphate surfactant component isabout 80:20 to about 85:15.
 13. The composition of claim 1 wherein (a)the amine surfactant component comprises polyoxyethylene tallowaminehaving about 8 to about 13 moles of ethylene oxide, (b) in the phosphatesurfactant component, R¹ is nonylphenol and m is about 4, and (c) thephosphate monoester is present in an amount that exceeds the amount ofthe phosphate diester.
 14. A method of controlling vegetation comprisingdiluting a composition of claim 1 in a suitable amount of water to forma sprayable composition, and spraying a herbicidally effective amount ofthe sprayable composition on foliage of the vegetation.